Vat dyestuffs of the anthraquinone series and process of making the same



Patented May 26, 1341 VAT DYESTUFFS 015 SERIES AND PROC SAME THE ANTHRAQUINONE ESS OF MAKING THE Wilhelm Bauer, Leverkusen-Wiesdorf, Germany, assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application 227,965. In Germany September 4,

rial N o. 1937 4 Claims.

My present invention relates to new and valuable vat dyestuffs of the anthraquinone series and to a process of making the same.

The new dyestufis correspond to the following general formula wherein X stands for a member of the group consisting of -NH or -S--, Z stands for a member of the group consisting of hydrogen and a group which does not effect solubility and R represents a radical of a vattable compound.

Preferred groups which do not effect solubility are, for instance, halogen atoms, alkoxy or aryloxy groups.

Preferred radicals of compounds which are capable of being vatted are anthraquinone radicals, though radicals of other vattable compounds, forinstanceofbenzanthrone, anthanthrone, violanthrone, pyrazole anthrone or of indigoid compounds are not excluded. These radicals may contain further substituents, for instance amino, acylamino, halogen or alkoxy groups.

My new dyestuifs represent dark colored crystals being sparingly soluble in organic solvents which dissolve easily in the hydrosulfite vat and dye vegetable fibers fast clear red to blue shades.

By using the dyestuffs in the rongalite-potash- 1 print they yield on cotton and artificial silk full prints of excellent fastness properties. 7

The new dyestuiTsare obtained by condensing in the presence of a suitable solvent, for instance nitrobenzene, anthraquinone-2.1- (N) -1'.2-(N) 6' aminobenzacridones or anthraquinone 2.1 (S) -1'.2'- (S) 6' aminobenzthioxanthones with monocarboxylic acid halides, preferably chlorides of compounds capable of being vatted. Suitable carboxylic acid halides of this type are, for instance, the carboxylic acid halides of the anthraquincne carboxylic acids, nitroor aminoanthraquinone carboxylic acids, 2 phenyl-anthraquinone-Bzi-oarboxylic acid, pyrazole-anthrone-2- carboxylic acid, 8-hydroxy-1.Z-naphthoxy-phen- September 1, 1938, Se-

.(Cl. 26ii-277) azine-Bz-carboxylic acid and carboxylic acids of indigoid compounds.

The anthraquinone- 2.1 (N) 1'.2' (N) 6 ammobenzeneacridones or -.2.1-(S) -1.2 (S) -6'- aminobenzthioxanthones respectively employed as starting materials can be obtained from the corresponding nitro derivatives by reduction or from the 6"-halogen derivatives by replacingthe halogen through the amino group or through acid amide radicals and saponification.

The following examples illustrate the invene tion, without, however, restricting it thereto, the

a parts being by weight:

Example 1 A mixture consisting of parts of anthraquinone-2.1 -(N) -1.2'-(N) 3'.6' dichlorobenzeneacridone, 70 parts of p-toluene-sulfamide, 20 parts of anhydrous potassium acetate, 700 parts of nitrobenzene and 2 parts of copper acetate is heated for 3 hours to 205 C. while stirring, the acetic acid thus formed being distilled ofi; The separated crystals are filtered with suction at a temperature of 55 0., washed with chlorobenzene, alcohol and water and then dried. The sulfamide forms violet needles. For saponification parts of this product are dissolved in 600 parts of concentrated sulfuric acid and heated to 60-70 C. for half an hour; then the reaction product is poured into water, stirred for one hour, filtered with suction, washed and dried. The anthraquinone-2.1-(N) -1'.2' (N) -3'- chloro- 6' aminobenzene-acridone forms blue needles. Then 35 parts of this aminoacridone, 30 parts of laminoanthraquinone-Z-carboxylic acid chloride and 800 par-ts of nitrcbenzene are heated to ISO- C. for one hour while stirring. The dyestufi" separating in a very good yield is filtered with suction in the-heat, washed with hot chlorobenzene and with alcohol and dried. It forms violet needles scarcely soluble in organic solvents yielding on the fiber from a dull-violet hydrosulfite vat clear bluish bordered shades of a good fastness to chlorine, boiling and light. In the rongalite-potash-print the dyestufi yields on cotton and artificial silk deep clear bordered shades of a very good fastness.

Example 2 tained, yielding from adull-violet vat more reddish bordo shades.

Anthraquinone-6'- aminobenzene-acridone can easily be obtained by causing anthraquinone-6- chlorobenzene-acridone (obtainable according to U. S. Patent 1,967,364) to react with p-toluenesulfamide and s'aponifying the reaction product with sulfuric acid. Another way to obtain the above product is by reducing anthraquinone-6- nitroacridone, the latter being prepared by causing 1-chloroanthraquinone-2-carboxylic acid to react with m-nitraniline in the usual manner.

Example 3 Example 4 A mixture of 30 parts of anthraquinone-2.1- (N) -1.2'-(N) -3' .4 .6 trichlorobenzene-acridone, 23.5 parts of p-toluene-sulfamide, 7.5 parts of glowed potassium acetate, 200 parts of nitrobenzene and 1 part of copper acetate is heated to 190 C. for 3 hours while stirring. The reaction product is filtered with suction at a temperature of 50 C., washed, dried and saponified by heating it for half an hour with the 6-fol quantity of concentrated sulfuric acid to 60-70 C. When poured into water, stirred, filtered with suction, washed and dried, the anthraquinone-3'.4'- dichloro-6'-aminobenzene-acridone is obtained in form of blue needles. p

A mixture of 16.3 parts of anthraquinone-3'.4'- dichloro-6'-aminobenzeneacridone, 13 parts of 1 -aminoanthraquinone-2-carboxylic acid chloride and 400'parts of nitrobenzene is heated for 2 hours to 170 C. while stirring, filtered with suction at 120 C. washed and dried. The reaction product represents a dyestufi forming violet needles, which are soluble in concentrated sulfuric acid with a red color and are unsoluble in organic solvents. It yields on cotton from a violet well as in the rongalite-potash-print clear an excellent fastness.

vat as ruby-red shades of Example 5 A mixture of 24 parts of 3'-phenoxy-6'-chloroanthraquinone 2.1 (N) -1.2'-(N) -benzeneacridone (obtainable according to U. S. Patent 2,097,- 112), 17 parts of p-toluenesulfamide, 5 parts of anhydrous potassium acetate, 1'75 parts of nitrobenzene and 1 part of copper acetate is heated for 2 hours to 210 C. while stirring. The reaction product is filtered with suction at a temperature of C., washed and dried. It is saponified by heating it for half an hour with the 10-fold quantity of a sulfuric acid to a temperature of C. On cooling the amine crystallizes out in form of the sulfate. It is filtered with suction with the aid of a suitable filter, washed with some 85% sulfuric acid, decomposed with water having an addition of alkali, filtered with suction, washed and dried. The 3'-phenoxy6-aminoanthraquinonebenzeneacridone represents a blue crystalline powder.

By aroylating the reaction product with the necessary quantity of 1-aminoanthraquinone-2- carboxylic acid chloride in nitrobenzene at a temperature of l70 C., a dyestufi is obtained in form of violet needles in a very good yield, being unsoluble in organic solvents and dyeing cotton from a dull-violet hydrosulfite vat strong violet shades of a very good fastness to chlorine, boiling and light.

Example 6 Example 7 chloro 6'- aminobenzenechlorides of the fol- Anthraquinone 3 acridone is acylated with the lowing acids:

Color of Color on Mad Result the vat cotton Anthraquinone-acarboxylie acid Violet needies Dull-violet--. Dull-ruby. l.9-pyrazole-enthrone-2-earboxylic acid. Brown needles- Violet Violet. Z-phenylanthraquinone-4-carboxylic acid Blue needles Brown-violet Ruby. Isopbthalic acid converted with one mol of l-amin0-5-benzoylamino- D a r k c r y s t al Dull-violet--- Brown.

anthraquinone. powder.

Cl. C O C ONH NH. O O C Hs B r o w n -bl :3 cl: Bordo Red-brown.

8-oxy-l.Z-naphthophenazine-Bz-carboxylic acid.

COOH

acid with fi-naphthoquinone-Eisulionlc ac alkali fusion.

crystal powder.

Example 8 2.4-dichloroaniline-6-sulfonic acid is transformed with the aid of the diazo compound by the Sandmeyers reaction in the 2.3.5-trichlorobenzene-l-sulfonic acid and the latter is transformed in the 2.3.5-trichlorophenylmercaptane by reducing the corresponding sulfochloride. When converted this mercaptane with 1-chioroanthraquinon-e-Z-carboxylic acid and subsequent formation of the thioxanthone ring there is obtained the anthraquinone 2.1-(S)-1.2'-(S)- 32426 trichlorobenzene-thioxanthone forming yellow needles and yielding on the fiber from a blue hydrosulfite vat greenish yellow shades.

A mixture of 44.5 parts of this anthraquinonetrichloro-thioxanthone, 30 parts of p-toluenesulfamide, parts of anhydrous potassium acetate, 300 parts of nitrobenzene and 1 part of copper acetate is heated to 205 C. for 2 hours. The product which separates on cooling is filtered with suction while being hot, washed, dried and saponified by heating it for half an hour with concentrated sulfuric acid at a temperature of 80 C. The amine obtained by pouring out the reaction mixture into water, filtering with suction, washing and drying, represents a blue powder.

21 parts of the anthraquinone-3'.4'-dichloro- 6' aminobenzene-thioxanthone thus obtained are stirred with parts of l-aminoanthraquinone-Z-carboxylic acid chloride in 400 parts of trichlorobenzene to 170 C. The dyestuff obtained is filtered with suction in the heat, washed and dried. It forms a. dark red crystal powder being unsoluble in organic solvents and yields on cotton from an olivish black-brown hydrosulfite vat a strong clear red of very good fastness to chlorine, boiling and light.

Example 9 A mixture of 42 parts of 6-ethoxy-2-thionaphthene 3-indol-indigo-7'-carboxylic acid chloride, 38 parts of anthraquinone-2.1-(N)- 1.2 (N) 32d dichloro 6 aminobenzeneacridone and 800 parts of trichlorobenzene is heated for 3 hours to 170 C. while stirring. The dyestuif then separated is filtered with suction, washed with organic solvents and dried It represents red-brown crystals being unsoluble in organic solvents The solution in concentrated sulfuric acid has a wine-red color. Red flakes are separated when diluted with water. After having been oxidized the dyestuff yields from a bordo-colored hydrosulfite vat on the fiber strong fast yellowish red shades.

The acid chloride mentioned above is obtained by causing the indigoid substance (prepared from G-ethoxythionaphthene and isatine-7-carboxylic acid according to U. S. Patent 1,890,718, Example 4) to react with thionyl chloride.

Example 10 By using 27.5 parts of anthraquinone-2.1-(N) l'.2" (N) -4'.6'-dichlorobenzene-acridone (obtainable from 3.5-dichloroaniline and 1-nitro-, 1-ha1ogenanthraquinone-Z-carboxylic acid respectively) instead of 30 parts of anthraquinone- 2.1 (N) 1'.2 (N) -3'.4.6'-trichlorobenzeneacridone, the anthraquinone-4'-chloro--6-aminobenzene-acridone is obtained in form of blue NH: O

. I H NH. 0 O-O 2. The dyestuff of the following formula NH; (I) NH. 0 o- A 3. The dyestuff of the following formula Cl KHN NH; O

NH.C O-OA Y 4. Vat dyestuffs of the general formula:

Z H2N H 0 EN t a/fi/ g wherein Z stands for a member of the group consisting of hydrogen and halogen, at least one of the Zs being halogen.

WILHELM BAUER. 

